2003/09/04 by R. K. Nesbet, Nesbet, R. K.
Chemical Engineering · Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced Physical and Chemical Molecular Interactions #Atomic Physics (physics.atom-ph) #Catalysis and Oxidation Reactions #Chemical Physics (physics.chem-ph) #Computational Physics (physics.comp-ph) #Condensed Matter (cond-mat) #FOS: Physical sciences #cond-mat #physics.atom-ph #physics.chem-ph #physics.comp-ph
paper · pdf · doi:10.48550/arxiv.cond-mat/0309111
Submitted to PhysRevB
arxiv created 2003/09/04 · openalex publication_date 2003/09/04 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
It is shown here that Kohn-Sham equations cannot be derived from Hohenberg-Kohn theory without an additional postulate. Assuming that a functional derivative with respect to total electron density exists leads in general to a theory inconsistent with the exclusion principle. A mathematically and physically correct variational theory of the Kohn-Sham model can be developed using functional derivatives with respect to orbital densities. These partial (Gâteaux) derivatives can be constructed explicitly from general N-electron theory and are defined throughout the orbital Hilbert space. This theory is consistent with the local density approximation (LDA), but does not in general imply multiplicative local exchange-correlation potentials. Progress beyond the LDA in condensed-matter physics requires development of methodology for nonlocal exchange and correlation potentials.